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    Print pastes
    21.
    发明专利
    Print pastes 未知

    公开(公告)号：GB1097770A

    公开(公告)日：1968-01-03

    申请号：GB5337365

    申请日：1965-12-16

    Applicant: BASF AG

    Inventor： WILHELM HANS ,  GULBINS KLAUS ,  MARX MATTHIAS ,  LANG GUENTER ,  SCHWINDT WOLFGANG ,  FAULHABER GERHARD

    IPC: D06P1/00

    Abstract: A print paste consists of a hydrocarbon liquid phase and an aqueous phase and contains as colouring agent a coloured copolymer prepared from 10 to 70 parts by weight of an ester of (a) acrylic or methacrylic acid, and (b) an aliphatic or cycloaliphatic alcohol having at least six carbon atoms; 1 to 40 parts of a comonomer containing an N-methylol group or N-methylol ether group; 1 to 12 parts of a copolymerizable dye; 4 to 15 parts of an alpha, beta-unsaturated mono- or di-carboxylic acid; 0 to 20 parts of an unsaturated polymerizable hydroxy compound and 0 to 84 parts of one or more other monomers; at least 50% of the free carboxyl groups in the copolymer having been neutralized by ammonia or nitrogenous organic bases. Suitable N-methylol monomers are the alkyl ethers of N-methylol arylamide and N-methylol methacrylamide and of carboxylic imides. Preferred dyes are azo and anthraquinone dyes. The organic base may be an aliphatic or heterocyclic amine. The print paste may include an aminoplast-forming substance and a cure catalyst. In Example 1, a xylene solution of a copolymer formed from alpha - ethylhexyl acrylate, N - butoxymethyl acrylamide, styrene, butanediol monoacrylate, acrylic acid and 2,4,5-trichloro-41-(N-ethyl-N-acryloyloxyethyl)-azobenzene which has been neutralized with dimethyl ethanolamine is mixed with water, NH4NO3 and white spirit. The azo dye may be replaced by 4-nitro-41-(N - ethyl - N - acryloyloxyethyl) - azobenzene or 1 - amino - 2 - isopropylcarboxy - 4 - acryloylaminoanthraquinone. In Example 2, N-butoxymethyl methacrylamide and hydroxy-5 - tertiary butyl - 41 - acryloylaminoazobenzene replace the N-methylol ether and the azo dye used in Example 1. The pastes are used to print fabrics (see Division D1).ALSO:An emulsion-thickened print paste consists of a hydrocarbon liquid phase, an aqueous phase and a coloured copolymer which has been prepared from: 10 to 70 parts by weight of an ester of (a) acrylic or methacrylic acid and (b) an aliphatic or cycloaliphatic alcohol having at least six carbon atoms; 1 to 40 parts of a comonomer containing an N-methylol or N-methylol ether group; 1 to 12 parts of a copolymerisable dye; 4 to 15 parts of an alpha, beta-unsaturated mono- or di-carboxylic acid; 0 to 20 parts of an unsaturated polymerisable hydroxy compound; and 0 to 84 parts of one or more other monomers; at least 50% of the free carboxyl groups in the copolymer having been neutralised by ammonia or nitrogenous organic bases. In Example 1 a xylene solution of a copolymer formed from alpha-ethylhexyl acrylate, N-butoxymethyl acrylamide, styrene butanediol monoacrylate, acrylic acid and 2, 4, 5-trichloro-4\sv - (N - ethyl- N -acryloyloxyethyl)-azobenzene which has been neutralised with dimethyl ethanolamine is mixed with water, NM4NO3 and white spirit. Cotton cloth is printed with the resulting paste and heated to yield orange prints. Red or violet prints are obtained when the azo dye is replaced by 4-nitro-4\sv-(N-ethyl-N-acryloyloxyethyl)-azobenzene or 1-amino-2-isopropylcarboxy - 4 - acryloylaminoanthraquinone. In Example 2, N-butoxymethyl methacrylanide and hydroxy - 5 - tertiarybutyl-4\sv-acryloylaminoazobenzene are used in place of p the N-methylol ether and azo dye in Example 1 and the paste is used to print cotton or polypropylene.

    Dyed and printed glass fibers and a process for dyeing and printing glass fibers
    26.
    发明专利
    Dyed and printed glass fibers and a process for dyeing and printing glass fibers 未知

    公开(公告)号：GB1082432A

    公开(公告)日：1967-09-06

    申请号：GB5046564

    申请日：1964-12-11

    Applicant: BASF AG

    Inventor： VESCIA MICHELE ,  SCHWINDT WOLFGANG ,  DIETRICH WERNER ,  PERKUHN ULRICH ,  FAULHABER GERHARD ,  WOLF HANS ,  WILHELM HANS

    IPC: C03C25/10 ,  C03C25/475 ,  D06P1/38

    Abstract: Glass fibres are dyed or printed with pigments using as a binder a film-forming polymer which becomes cross-linked under the influence of a proton-acceptor and using an amino-silane or a hydrocarbon wax as an agent having hydrophobic action to promote adhesion between the binder and the glass surface, the process being carried out in the presence of a proton-acceptor, and the treated fibres being finally dried and heated. The polymers are those having groups, for example amino or hydroxy groups, which by means of proton acceptors can enter into covalent bonds with themselves or other groups. The preferred polymers are copolymers bearing hydrocarbon radicals as side chains in which a halogen atom and a hydroxyl group are attached to two adjacent carbon atoms, particularly a polymer obtained by co-polymerising 2-hydroxy-3-chloropropyl acrylate with other monomers. The proton-acceptor may be an alkali metal hydroxide, carbonate or bicarbonate, amonia or an organic amine; it may be provided as the alkali present in the glass. The glass fibres may be treated as such, mixed with other fibres or in the form of fabric. In the treatment, the various components can be applied separately or in combination. Examples illustrate the use of copper phthalocyanine, azo dyes and carbon black as the pigments.

    Print pastes
    27.
    发明专利
    Print pastes 未知

    公开(公告)号：GB1079718A

    公开(公告)日：1967-08-16

    申请号：GB4876465

    申请日：1965-11-17

    Applicant: BASF AG

    Inventor： WILHELM HANS ,  MARX MATTHIAS ,  FAULHABER GERHARD ,  SCHWINDT WOLFGANG

    IPC: C08F20/58 ,  D06M15/263 ,  D06M15/29 ,  D06P1/44

    Abstract: Print pastes for textiles and other substrates comprise an oil-in-water emulsion containing a pigment or vat dye and, as a binder, a water-soluble copolymer of:-(1) to 70 parts by weight of a neutral ester of an a , b -ethylenically unsaturated mono-or di-carboxylic acid and an aliphatic or cycloaliphatic alcohol having at least 6 carbon atoms; (2) 1 to 40 parts by weight of an ethylenically unsaturated polymerizable nitrogenous compound containing at least one N-methylol ether group; (3) 4 to 15 parts by weight of a polymerizable a , b -ethylenically unsaturated mono- or di-carboxylic acid; (4) 0 to 20 parts by weight of an ethylenically unsaturated polymerizable hydroxy compound; and (5) 0 to 70 parts by weight of another ethylenically unsaturated monomer; the total amount or major proportion of the free carboxylic groups in the copolymer having been neutralized by ammonia or a nitrogenous organic base (e.g. methylamine, triethylamine, dimethy-ethanol-amine, triethanolamine, piperidine or morpholine). Suitble monomer components of the copolymer include (1) esters of acrylic, methacrylic, crotonic, maleic or fumaric acid with hexanol, heptanol, octanol, isooctanol, dodecanol, a -ethylhexanol, cyclohexanol or hexanediol; (2) N-methylol ethers of unsaturated amides and imides and unsaturated compounds containing a ureido, aminotriazine, dicyanodiamide, carbamic acid, thiocarbamic acid; glyoxal-monoureine or glyoxal diureine group; (3) crotonic, citraconic, itaconic, mesaconic, maleic, fumaric and, preferably, acrylic or methacrylic acid; (4) monoesters of polyhydric alcohols and ethylenically unsaturated carboxylic acids, monovinyl ethers of polyhydric alcohols, allyl alcohol and hydroxy-containing bicycloheptene derivatives; (5) styrene, esters of acrylic or methacrylic acid with alcohols having up to 5 carbon atoms, vinyl esters (including versatic esters), butadiene, isoprene, acrylonitrile, methacrylonitrile, acrylamide and methacrylamide and their N-alkyl derivatives, vinyl chloride, vinylidene chloride, vinyl ethyl ether, vinyl ethyl ketone, N-vinylimidazole, N-vinyl pyrrolidone and N-vinyl caprolactam. White spirit or mineral spirit gasoline fractions may be used as the oil phase of the emulsion. Pigments exemplified are red iron oxide, aluminium poweder and copper phthalocyanine. The print pastes may optionally include cross-linking or curing agents such as aminoplasts and ammonium thiocyanate. In an example the binder comprises a copolymer of a -ethylhexyl acrylate, N-(n-butoxymethyl)-acrylamide, acrylic acid, 1, 4-butanediol monoacrylate and styrene, neutralized with dimethylethanolamine.ALSO:Print pastes for textiles, e.g. cotton cloth, and other substrates comprise an oil-in-water emulsion containing a pigment or vat dye and, as a binder, a water-soluble copolymer of:- (1) 10 to 70 parts by weight of a neutral ester of an a ,b -ethylenically unsaturated mono- or dicarboxylic acid and an aliphatic or cycloaliphatic alcohol having at least 6 carbon atoms; (2) 1 to 40 parts by weight of an ethylenically unsaturated polymerisable nitrogenous compound containing at least one N-methylol ether group; (3) 4 to 15 parts by weight of a polymerisable a ,b -ethylenically unsaturated mono- or di-carboxylic acid; (4) 0 to 20 parts by weight of an ethylenically unsaturated polymerisable hydroxy compound; and (5) 0 to 70 parts by weight of another ethylenically unsaturated monomer; the total amount or major proportion of the free carboxylic groups in the copolymer having been neutralised by ammonia or a nitrogenous organic base (e.g. methylamine, triethylamine, dimethyl ethanolamine, triethanolamine, piperidine or morpholine). White spirit or mineral spirit gasoline fractions may be used as the oil phase of the emulsion. Pigments exemplified are red iron oxide, aluminium powder and copper phthalocyanine. The print pastes may optionally include cross-linking or curing agents such as aminoplasts and ammonium thiocyanate. In an Example the binder comprises a copolymer of a -ethylhexyl acrylate, N-(n-butoxymethyl)-acrylamide, acrylic acid, 1,4-butanediol monoacrylate and styrene, neutralised with dimethylethanolamine.

    Binder and process for flocking fibrous material
    29.
    发明专利
    Binder and process for flocking fibrous material 未知

    公开(公告)号：GB1011810A

    公开(公告)日：1965-12-01

    申请号：GB2553963

    申请日：1963-06-27

    Applicant: BASF AG

    Inventor： CRAEMER KARL ,  SCHWINDT WOLFGANG ,  WOLF HANS ,  WILHELM HANS ,  ZAUNBRECHER HORST

    IPC: D04H11/00 ,  D06M15/263 ,  D06M15/29 ,  D06M23/10

    Abstract: A binder for flocking fibrous material comprises a thickened aqueous dispersion of a self-cross-linking copolymer and from 3 to 30% by weight of the total binder of an organic liquid which exerts a swelling, but no dissolving, action on the copolymer. Preferred copolymers are those made from an alkyl acrylate or methacrylate, acrylonitrile or methacrylonitrile N-methylol acrylamide or methacrylamide, an unsaturated carboxylic acid and, optionally, other monomers. Suitable organic liquids are aliphatic halohydrocarbons, aromatic hydrocarbons, ketones, esters and amides. Also present in the compositions may be water-dispersible aminoplast condensates, and catalysts for the cross-linking of the copolymers and condensation of the aminoplasts. Coatings formed from the compositions are cross-linked by heating above 80 DEG C. The examples describe the following compositions: (1) an ammonia-neutralized aqueous dispersion of a copolymer of n-butyl acrylate, ethyl acrylate, acrylonitrile, acrylic acid and N-methylolmethacrylamide containing trichloroethylene, dimethylolurea dimethyl ether urea, a sperm oil alcohol/ethylene oxide condensate and ammonium thiocyanate; (2) an ammonia-neutralized aqueous dispersion of a copolymer of isobutyl acrylate, acrylonitrile, N-methylolacrylamide and acrylic acid containing perchloroethylene, the dimethylol compound of butanediol diurethane, a sperm oil alcohol/ethylene oxide condensate and ammonium thiocyanate; (3) an ammonia-neutralized aqueous dispersion of a copolymer of n-butyl acrylate, styrene, acrylonitrile, acrylic acid and the N-methylol ethyl ether of methacrylamide, containing cyclohexanone, a urea-formaldehyde condensate, methyl cellulose, a sperm oil alcohol/ethylene oxide condensate and diammonium phosphate; and (4) an ammonia-neutralized aqueous dispersion of a copolymer of n-butyl acrylate, methyl acrylate, acrylonitrile, divinyl benzene N-methylolmethacrylamide and acrylic acid containing a urea-formaldehyde condensate, trichloroethylene, methyl cellulose, urea, ammonium chloride and ammonium thiocyanate. Specification 1,011,809 is referred to.ALSO:Fabrics are flocked by applying thereto an adhesive comprising a thickened aqueous dispersion of a self-crosslinking copolymer and from 3-30% by weight of the total composition of an organic liquid which exerts a swelling, but no dissolving, action on the copolymer (see Division C3), flocking the coated fabric, and then heating the assembly at a temperature greater than 80 DEG C. to cross-link the copolymer. Also present in the compositions may be water-dispersible aminoplast condensates, and catalysts for the cross-linking of the copolymers and condensation of the aminoplasts. The examples describe the following processes: (1) applying to jute fabric and bonded cotton non-woven fabric an ammonia-neutralized aqueous dispersion of a copolymer of n-butyl acrylate, ethyl acrylate, acrylic acid and N-methylolmethacrylamide containing trichloroethylene and dimethylolurea dimethyl ether, flocking the coated fabrics with nylon-6 flock, and heating at 130 DEG C., (2) applying to cotton cloth, which has been given a waterproof finish with paraffin emulsion, an ammonia-neutralized aqueous dispersion of a copolymer of isobutyl acrylate, acrylonitrile, N-methylolacrylamide and acrylic acid containing the dimethylol compound of butanediol diurethane and perchloroethylene, flocking the coated cloth with viscose flock, and heating at 140 DEG C., (3) applying to jute fabric, which has been coated with polyvinyl chloride paste and then gelled, an ammonia-neutralized copolymer of n-butyl acrylate, styrene, acrylonitrile, the N-methylol ethyl ether of methacrylamide and acrylic acid containing a urea-formaldehyde condensate and cyclohexanone, flocking the fabric with polyamide flock and heating at 120 DEG C., and (4) applying to a cotton fabric, which has been laminated with polyvinyl chloride foam, an ammonia-neutralized aqueous dispersion of a copolymer of n-butyl acrylate, methyl acrylate, acrylonitrile, acrylic acid, N-methylol methacrylamide and divinyl benzene containing a urea-formaldehyde condensate and trichloroethylene, flocking the fabric with polyamide flock, and heating at slightly above 80 DEG C. Specification 1,011,809 is referred to.

    Binder and process for flocking surfaces
    30.
    发明专利
    Binder and process for flocking surfaces 未知

    公开(公告)号：GB1011809A

    公开(公告)日：1965-12-01

    申请号：GB2553863

    申请日：1963-06-27

    Applicant: BASF AG

    Inventor： CRAEMER KARL ,  SCHWINDT WOLFGANG ,  WILHELM HANS ,  WOLF HANS ,  ZAUNBRECHER HORST

    IPC: D04H11/00 ,  D06M15/39

    Abstract: Binders for flocking surfaces comprise, for each 100 parts by weight: (a) 20 to 45 parts by weight of one or more copolymers prepared by polymerization in an aqueous dispersion at a maximum pH value of 5 of a mixture of monomers consisting of: (i) 40-80% by weight of one or more C2-C4 acrylates and/or methacrylates, (ii) 10-35% by weight of acrylonitrile and/or methacrylonitrile, (iii) 3-6% by weight of N-methylol acrylamide and/or methacrylamide, (iv) 0.5-5% by weight of a polymerizable carboxylic acid, and (v) 0-40% by weight of one or more other unsaturated compounds, the copolymer being thickened by the addition of an alkaline substance; (b) 3 to 30 parts by weight of a water-soluble or -dispersible aminoplast-forming substance containing N-methyl or N-methylol ether groups; (c) 0.1-5 parts of at least one acidic condensation catalyst; and, optionally, (d) conventional amounts of one or more conventional flock binder additives, the excess above the total quantity included in (a)-(d) needed to give a total of 100 parts by weight representing the quantity of water present in the aqueous dispersion. The examples describe compositions in which there are used as components (a) ammonia - neutralized aqueous dispersions of n - butyl acrylate/ethyl acrylate/acrylonitrile/N - methylolmethacrylamide/acrylic acid, isobutyl acrylate/acrylonitrile/N - methylolacrylamide/methacryli acid, and n-butyl acrylate/acrylonitrile/styrene/N - methylolmethacryl amide/acrylic acid copolymers, as components (b) dimethylolurea dimethyl ether and the dimethylol compound of butanedioldiurethane, as components (c) ammonium nitrate and thiocyanate, and as components (d) a sperm oil alcohol/ethylene oxide condensate and the sodium salt of the acid sulphate thereof, cellulose methyl ether, dioctyl phthalate, urea, an azo dyestuff, and kerosene. The compositions are cross-linked, after a flocking operation, by heating at temperatures above 90 DEG C.ALSO:Flocked surfaces are produced by applying fibrous flock to the surface of a porous material on which has been deposited a binder comprising, in an aqueous medium, (a) a copolymer of (i) one or more C2-C4 acrylates and/or methacrylates, (ii) acrylonitrile and/or methacrylonitrile, (iii) N-methylol acrylamide and/or methacrylamide, (iv) an unsaturated carboxylic acid, and, optionally, (v) one or more other unsaturated compounds, (b) a water-soluble or -dispersible aminoplast-forming substance containing N-methylo or N-methylol ether groups, (c) an acidic condensation catalyst, and, optionally, (d) conventional flock binder additives (see Division C3). The examples describe flocking the surfaces of jute and cotton fabrics with nylon-6 fibres, and surfaces of polyamide, polyester, viscose rayon and cellulose acetate fabrics with viscose rayon fibres, the fabric surfaces being printed with compositions in which there are used as components (a) ammonia-neutralized aqueous dispersions of n-butyl acrylate/ethyl acrylate/acrylonitrile/N-methylolmethacrylamide/acrylic acid, isobutyl acrylate / acrylonitrile / N-methylolacrylamide/methacrylic acid, and n-butyl acrylate/acrylonitrile/styrene/N-methylolacrylamide/acrylic acid copolymers, as components (b) dimethylol urea dimethyl ether and the dimethylol compound of butanedioldiurethane, as components (c) ammonium nitrate and thiocyanate, and as components (d) a sperm oil alcohol/ethylene oxide condensate and the sodium salt of the acid sulphate thereof, cellulose methyl ether, dioctyl phthalate, urea, an azo dyestuff and kerosene. After flocking, the binders are cross-linked by heating to temperatures above 90 DEG C.

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